Spectroscopic characterization of the complex of vinyl radical and carbon dioxide: Matrix isolation and ab initio study.

Abstract

We report on the preparation and vibrational characterization of the C2H3⋯CO2 complex, the first example of a stable intermolecular complex involving vinyl radicals. This complex was prepared in Ar and Kr matrices using UV photolysis of propiolic acid (HC3OOH) and subsequent thermal mobilization of H atoms. This preparation procedure provides vinyl radicals formed exclusively as a complex with CO2, without the presence of either CO2 or C2H3 monomers. The absorption bands corresponding to the ν5(C2H3), ν7(C2H3), ν8(C2H3), ν2(CO2), and ν3(CO2) modes of the C2H3⋯CO2 complex were detected experimentally. The calculations at the UCCSD(T)/L2a level of theory predict two structures of the C2H3⋯CO2 complex with Cs and C1 symmetries and interaction energies of -1.92 and -5.19 kJ mol-1. The harmonic vibrational frequencies of these structures were calculated at the same level of theory. The structural assignment of the experimental species is not straightforward because of rather small complexation-induced shifts and matrix-site splitting of the bands (for both complex and monomers). We conclude that the C1 structure is the most probable candidate for the experimental C2H3⋯CO2 complex based on the significant splitting of the bending vibration of CO2 and on the energetic and structural considerations.